EP2723312B2 - Tapiokastärke in silikonelastomer-haltigen kosmetischen zubereitungen - Google Patents
Tapiokastärke in silikonelastomer-haltigen kosmetischen zubereitungen Download PDFInfo
- Publication number
- EP2723312B2 EP2723312B2 EP12727667.3A EP12727667A EP2723312B2 EP 2723312 B2 EP2723312 B2 EP 2723312B2 EP 12727667 A EP12727667 A EP 12727667A EP 2723312 B2 EP2723312 B2 EP 2723312B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- ethylhexyl
- acid
- sio
- bis
- monovalent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Not-in-force
Links
- 238000002360 preparation method Methods 0.000 title claims description 38
- 229920002379 silicone rubber Polymers 0.000 title claims description 22
- 239000002537 cosmetic Substances 0.000 title claims description 18
- 240000003183 Manihot esculenta Species 0.000 title claims description 7
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 title claims description 7
- 229920002472 Starch Polymers 0.000 title claims description 7
- 235000019698 starch Nutrition 0.000 title claims description 7
- 239000008107 starch Substances 0.000 title claims description 7
- -1 3-(4-(2,2-bis ethoxycarbonylvinyl)phenoxy)propenyl Chemical group 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 35
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 21
- 229920001971 elastomer Polymers 0.000 claims description 21
- 239000000806 elastomer Substances 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 19
- 239000000499 gel Substances 0.000 claims description 18
- 239000004904 UV filter Substances 0.000 claims description 12
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- OSCJHTSDLYVCQC-UHFFFAOYSA-N 2-ethylhexyl 4-[[4-[4-(tert-butylcarbamoyl)anilino]-6-[4-(2-ethylhexoxycarbonyl)anilino]-1,3,5-triazin-2-yl]amino]benzoate Chemical compound C1=CC(C(=O)OCC(CC)CCCC)=CC=C1NC1=NC(NC=2C=CC(=CC=2)C(=O)NC(C)(C)C)=NC(NC=2C=CC(=CC=2)C(=O)OCC(CC)CCCC)=N1 OSCJHTSDLYVCQC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- FMRHJJZUHUTGKE-UHFFFAOYSA-N Ethylhexyl salicylate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1O FMRHJJZUHUTGKE-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 229910020388 SiO1/2 Inorganic materials 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 238000004132 cross linking Methods 0.000 claims description 5
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 5
- 229910020447 SiO2/2 Inorganic materials 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229940068171 ethyl hexyl salicylate Drugs 0.000 claims description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 4
- FMJSMJQBSVNSBF-UHFFFAOYSA-N octocrylene Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC(CC)CCCC)C1=CC=CC=C1 FMJSMJQBSVNSBF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 4
- JGUMTYWKIBJSTN-UHFFFAOYSA-N 2-ethylhexyl 4-[[4,6-bis[4-(2-ethylhexoxycarbonyl)anilino]-1,3,5-triazin-2-yl]amino]benzoate Chemical compound C1=CC(C(=O)OCC(CC)CCCC)=CC=C1NC1=NC(NC=2C=CC(=CC=2)C(=O)OCC(CC)CCCC)=NC(NC=2C=CC(=CC=2)C(=O)OCC(CC)CCCC)=N1 JGUMTYWKIBJSTN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- UVCJGUGAGLDPAA-UHFFFAOYSA-N ensulizole Chemical compound N1C2=CC(S(=O)(=O)O)=CC=C2N=C1C1=CC=CC=C1 UVCJGUGAGLDPAA-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- HEOCBCNFKCOKBX-RELGSGGGSA-N (1s,2e,4r)-4,7,7-trimethyl-2-[(4-methylphenyl)methylidene]bicyclo[2.2.1]heptan-3-one Chemical compound C1=CC(C)=CC=C1\C=C/1C(=O)[C@]2(C)CC[C@H]\1C2(C)C HEOCBCNFKCOKBX-RELGSGGGSA-N 0.000 claims description 2
- OIQXFRANQVWXJF-QBFSEMIESA-N (2z)-2-benzylidene-4,7,7-trimethylbicyclo[2.2.1]heptan-3-one Chemical compound CC1(C)C2CCC1(C)C(=O)\C2=C/C1=CC=CC=C1 OIQXFRANQVWXJF-QBFSEMIESA-N 0.000 claims description 2
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 claims description 2
- CENPSTJGQOQKKW-UHFFFAOYSA-N 2,4,6-tris(4-phenylphenyl)-1,3,5-triazine Chemical compound C1=CC=CC=C1C1=CC=C(C=2N=C(N=C(N=2)C=2C=CC(=CC=2)C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC=CC=2)C=C1 CENPSTJGQOQKKW-UHFFFAOYSA-N 0.000 claims description 2
- WSSJONWNBBTCMG-UHFFFAOYSA-N 2-hydroxybenzoic acid (3,3,5-trimethylcyclohexyl) ester Chemical compound C1C(C)(C)CC(C)CC1OC(=O)C1=CC=CC=C1O WSSJONWNBBTCMG-UHFFFAOYSA-N 0.000 claims description 2
- KKJKXQYVUVWWJP-UHFFFAOYSA-N 4-[(4,7,7-trimethyl-3-oxo-2-bicyclo[2.2.1]heptanylidene)methyl]benzenesulfonic acid Chemical class CC1(C)C2CCC1(C)C(=O)C2=CC1=CC=C(S(O)(=O)=O)C=C1 KKJKXQYVUVWWJP-UHFFFAOYSA-N 0.000 claims description 2
- WYWZRNAHINYAEF-UHFFFAOYSA-N Padimate O Chemical compound CCCCC(CC)COC(=O)C1=CC=C(N(C)C)C=C1 WYWZRNAHINYAEF-UHFFFAOYSA-N 0.000 claims description 2
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- 239000007983 Tris buffer Substances 0.000 claims description 2
- DTVQVQGCVNNOSX-UHFFFAOYSA-N bis(2-ethylhexyl) 2-[(4-methoxyphenyl)methylidene]propanedioate Chemical compound CCCCC(CC)COC(=O)C(C(=O)OCC(CC)CCCC)=CC1=CC=C(OC)C=C1 DTVQVQGCVNNOSX-UHFFFAOYSA-N 0.000 claims description 2
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 claims description 2
- HUVYTMDMDZRHBN-UHFFFAOYSA-N drometrizole trisiloxane Chemical compound C[Si](C)(C)O[Si](C)(O[Si](C)(C)C)CC(C)CC1=CC(C)=CC(N2N=C3C=CC=CC3=N2)=C1O HUVYTMDMDZRHBN-UHFFFAOYSA-N 0.000 claims description 2
- HEAHZSUCFKFERC-UHFFFAOYSA-N ecamsule Chemical compound CC1(C)C2CCC1(CS(O)(=O)=O)C(=O)C2=CC(C=C1)=CC=C1C=C1C(=O)C2(CS(O)(=O)=O)CCC1C2(C)C HEAHZSUCFKFERC-UHFFFAOYSA-N 0.000 claims description 2
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- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 2
- MJVGBKJNTFCUJM-UHFFFAOYSA-N mexenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=C(C)C=C1 MJVGBKJNTFCUJM-UHFFFAOYSA-N 0.000 claims description 2
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 claims description 2
- LXTZRIBXKVRLOA-UHFFFAOYSA-N padimate a Chemical compound CCCCCOC(=O)C1=CC=C(N(C)C)C=C1 LXTZRIBXKVRLOA-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
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- 150000003254 radicals Chemical class 0.000 claims 2
- YBGZDTIWKVFICR-JLHYYAGUSA-N Octyl 4-methoxycinnamic acid Chemical compound CCCCC(CC)COC(=O)\C=C\C1=CC=C(OC)C=C1 YBGZDTIWKVFICR-JLHYYAGUSA-N 0.000 claims 1
- 125000003342 alkenyl group Chemical group 0.000 claims 1
- YKPUWZUDDOIDPM-SOFGYWHQSA-N capsaicin Chemical compound COC1=CC(CNC(=O)CCCC\C=C\C(C)C)=CC=C1O YKPUWZUDDOIDPM-SOFGYWHQSA-N 0.000 claims 1
- 150000001723 carbon free-radicals Chemical class 0.000 claims 1
- FDATWRLUYRHCJE-UHFFFAOYSA-N diethylamino hydroxybenzoyl hexyl benzoate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1O FDATWRLUYRHCJE-UHFFFAOYSA-N 0.000 claims 1
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- ARCJQKUWGAZPFX-UHFFFAOYSA-N stilbene oxide Chemical compound O1C(C=2C=CC=CC=2)C1C1=CC=CC=C1 ARCJQKUWGAZPFX-UHFFFAOYSA-N 0.000 description 1
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- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
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- 230000037072 sun protection Effects 0.000 description 1
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- 229960003080 taurine Drugs 0.000 description 1
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- 229940116411 terpineol Drugs 0.000 description 1
- XMRSTLBCBDIKFI-UHFFFAOYSA-N tetradeca-1,13-diene Chemical compound C=CCCCCCCCCCCC=C XMRSTLBCBDIKFI-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- RTKIYNMVFMVABJ-UHFFFAOYSA-L thimerosal Chemical compound [Na+].CC[Hg]SC1=CC=CC=C1C([O-])=O RTKIYNMVFMVABJ-UHFFFAOYSA-L 0.000 description 1
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- 235000010384 tocopherol Nutrition 0.000 description 1
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- RUVINXPYWBROJD-ONEGZZNKSA-N trans-anethole Chemical compound COC1=CC=C(\C=C\C)C=C1 RUVINXPYWBROJD-ONEGZZNKSA-N 0.000 description 1
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- LOIYMIARKYCTBW-OWOJBTEDSA-N trans-urocanic acid Chemical compound OC(=O)\C=C\C1=CNC=N1 LOIYMIARKYCTBW-OWOJBTEDSA-N 0.000 description 1
- LOIYMIARKYCTBW-UHFFFAOYSA-N trans-urocanic acid Natural products OC(=O)C=CC1=CNC=N1 LOIYMIARKYCTBW-UHFFFAOYSA-N 0.000 description 1
- 230000036572 transepidermal water loss Effects 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 229940040064 ubiquinol Drugs 0.000 description 1
- QNTNKSLOFHEFPK-UPTCCGCDSA-N ubiquinol-10 Chemical compound COC1=C(O)C(C)=C(C\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CCC=C(C)C)C(O)=C1OC QNTNKSLOFHEFPK-UPTCCGCDSA-N 0.000 description 1
- 229940035936 ubiquinone Drugs 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- PLSAJKYPRJGMHO-UHFFFAOYSA-N ursolic acid Natural products CC1CCC2(CCC3(C)C(C=CC4C5(C)CCC(O)C(C)(C)C5CCC34C)C2C1C)C(=O)O PLSAJKYPRJGMHO-UHFFFAOYSA-N 0.000 description 1
- 229940096998 ursolic acid Drugs 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 229940117960 vanillin Drugs 0.000 description 1
- 230000024883 vasodilation Effects 0.000 description 1
- 239000010679 vetiver oil Substances 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 235000020334 white tea Nutrition 0.000 description 1
- FJHBOVDFOQMZRV-XQIHNALSSA-N xanthophyll Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CC(O)CC1(C)C)C=CC=C(/C)C=CC2C=C(C)C(O)CC2(C)C FJHBOVDFOQMZRV-XQIHNALSSA-N 0.000 description 1
- 235000010930 zeaxanthin Nutrition 0.000 description 1
- 239000001775 zeaxanthin Substances 0.000 description 1
- 229940043269 zeaxanthin Drugs 0.000 description 1
- 235000011478 zinc gluconate Nutrition 0.000 description 1
- 239000011670 zinc gluconate Substances 0.000 description 1
- 229960000306 zinc gluconate Drugs 0.000 description 1
- 229940043810 zinc pyrithione Drugs 0.000 description 1
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
- IHPKGUQCSIINRJ-UHFFFAOYSA-N β-ocimene Natural products CC(C)=CCC=C(C)C=C IHPKGUQCSIINRJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/895—Polysiloxanes containing silicon bound to unsaturated aliphatic groups, e.g. vinyl dimethicone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/062—Oil-in-water emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
- A61K8/732—Starch; Amylose; Amylopectin; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
Definitions
- the present invention relates to a cosmetic preparation with UV filters, silicone elastomer gels and tapioca starch.
- active ingredients are used on the one hand, which stimulate the activity of the skin cells, for example, but more and more UV filters are used, which particularly block the UVA rays responsible for skin aging. All of these ingredients represent a major challenge for pleasant sensor technology, since after the volatile constituents of the formulation have evaporated, they remain on the skin as a film, where they are sensed by the consumer. The palpable residues are often described negatively and prevent the feeling that the product is completely "absorbed" in the skin.
- silicone compounds and powder raw materials should be mentioned here, as they have the sticky feeling of e.g. Can mask glycerin or the oily / greasy appearance of many lipids or UV filters.
- This medium is preferably a low-viscosity, preferably also volatile silicone.
- This class of raw materials provides a powdery / dry, velvety / silky skin feel after spreading and, depending on the type of formulation, can mask oily / greasy and / or sticky raw materials.
- silicone elastomers are more pronounced in W / O emulsions than in O / W emulsions, because in this case they are in the outer, hydrophobic phase and can therefore be perceived directly by the sensor.
- These formulations are particularly rich and therefore not suitable for all consumer groups. Consumers who have normal to combination skin tend to place much less value on a rich product than people with dry skin. This is particularly because the richness is connected with the care and protection of the skin.
- a light facial care product for normal to combination skin which has at least a sun protection factor of 15 with corresponding UVA protection and preferably contains at least 10% glycerol in order to meet consumer expectations with regard to protection against aging of the skin by UV radiation and on moisture supply.
- the product should soak completely into the skin quickly and feel natural at all times. Desired additional benefits are e.g. an efficiently adjustable consistency for presentation in the crucible or a high water resistance in order to improve the product properties e.g. to keep even when sweating or other activities related to water.
- a disadvantage of the prior art is in particular the fact that the water resistance of preparations containing UV filters can usually only be guaranteed by the use of film formers (e.g. polyvinylpyrrolidone).
- film formers e.g. polyvinylpyrrolidone
- the use of such film formers leads to a sticky, unpleasant feeling on the skin.
- When used on the beach, such preparations also lead to increased sand adhesion.
- Silicone elastomer gels that have a positive effect on the feeling on the skin can at best insufficiently compensate for this effect.
- compositions of the present invention are characterized in that the preparation contains at least 5% by weight, based on the total weight of the preparation, of UV filters.
- the silicone elastomer gels which are advantageous according to the invention are crosslinked, optionally substituted organopolysiloxanes which are swollen in a suitable carrier medium.
- the crosslinking can have been carried out using all common methods and crosslinkers.
- Carrier media can e.g. cyclic or linear silicones and organic lipids.
- an additional second SusSi-H-containing polysiloxane is present, which is selected from HR 1 2 SiO (R 1 2 SiO) e SiR 1 2 H, HR 1 2 SiO (R 1 2 SiO) a (R 1 HSiO) d SiR 1 2 H and mixtures thereof, wherein each R 1 is independently a monovalent hydrocarbon group having 1 to 30 carbon atoms, a is 265 to 2000 and d is 1 to 250 and e is 0 to 250 is, the second ⁇ Si-H containing polysiloxane are present in a molar ratio of> 0 to 20.
- (b) is selected from 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1 , 11-dodecadiene, 1,13-tetradecadiene and 1,19-eicosadiene, 1,3-butadiene, 1,5-hexadiene (dipropargyl) and 1, hexen-5-in.
- the molar ratio of (a) to (b) is in the range from 0.7: 1 to 1.3: 1.
- siloxane elastomers according to the invention can be purchased, for example, from Dow Corning under the trade name DC 9040, 9041 or 9045.
- this siloxane elastomer C) according to the invention is used in a concentration of 5 to 25% by weight and preferably in a concentration of 10 to 15% by weight, in each case based on the total weight of the composition.
- the preparation according to the invention contains one or more further UV filters selected from the group of the compounds 2-phenylbenzimidazole-5-sulfonic acid and / or their salts; Phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid salts; 1,4-di (2-oxo-10-sulfo-3-bornylidenemethyl) benzene and its salts; 4- (2-oxo-3-bornylidenemethyl) benzenesulfonic acid salts; 2-methyl-5- (2-oxo-3-borny-lidenemethyl) sulfonic acid salts; 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol); 2- (2H-benzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [1,3,3,3
- Biochinones in particular ubiquinone Q10, isoflavone and isoflavonoids, genistein, arctiin, cardiolipin, lipoic acid, anti-freezing proteins, hop and hop-malt extracts and / or substances which promote the restructuring of the connective tissue, isoflavonoids and isoflavonoid substances are therefore considered to be particularly preferred active substances.
- plant extracts such as soy and clover extracts, which can also be used very well in the preparations and skin-covering matrices according to the invention.
- the combination product according to the invention is particularly suitable, active ingredients for supporting skin functions in dry skin, such as, for example, vitamin C, biotin, creatine, creatinine, propionic acid, glycerol, green tea extracts, white tea extracts or solutions, to use.
- active ingredients for supporting skin functions in dry skin, such as, for example, vitamin C, biotin, creatine, creatinine, propionic acid, glycerol, green tea extracts, white tea extracts or solutions, to use.
- active ingredients for supporting skin functions in dry skin, such as, for example, vitamin C, biotin, creatine, creatinine, propionic acid, glycerol, green tea extracts, white tea extracts or solutions, to use.
- Active substances such as sericosides, various extracts of liquorice, licochalcone A, silymarin or silyphos, flavonoids, dexpanthenol, ethanol, inhibitors of prostaglandin metabolism, especially cyclooxygenase, and leukotriene metabolism, especially 5-lipoxygenase, but also 5- Lipoxygenase Inhibitor Proteins, FLAP.
- the incorporation of pigmentation modulators also proved to be advantageous.
- Active substances that reduce the pigmentation of the skin and thus lead to a cosmetically desired lightening of the skin and / or reduce the appearance of age spots and / or brighten existing age spots such as tyrosine sulfate, vitamin C, lipoic acid and liponamide, various extracts of the Licorice, kojic acid, hydroquinone, arbutin, fruit acids, especially alpha-hydroxy acids (AHAs), bearberry (Uvae ursi), ursolic acid, ascorbic acid, green tea extracts, aminoguanidine and / or pyridoxamine.
- the nutritional supplements, preparations or matrices according to the invention have proven to be an excellent basis for active substances which bring about an intensified / faster tanning of the skin (advanced glycation end products (AGE), lipofuscins, nucleic acid oligonucleotides, purines and pyrimidines, NO-releasing substances, be it with or without the influence of UV light.
- active substances which bring about an intensified / faster tanning of the skin
- AGE intensity glycation end products
- lipofuscins lipofuscins
- nucleic acid oligonucleotides nucleic acid oligonucleotides
- purines and pyrimidines purines and pyrimidines
- NO-releasing substances be it with or without the influence of UV light.
- Active substances that are also suitable for use are, for example, folic acid, phytoene, urea, D-biotin, coenzyme Q10, flavone glycosides such as e.g. ⁇ -Glucosylrutin, carnitine, polydocanol, natural and synthetic isoflavonoids, in particular genistein, flavonoids, carotenoids, creatine, creatinine, taurine, ascorbic acid and their derivatives, oxygen, tocopherol and its esters, dihydroxyacetone, 8-hexadecen-1,16-dicarboxylic acid, long Hyaluronic acids (ie with an average molecular weight of 1 million to 3 million daltons) and short-chain hyaluronic acids (ie with an average molecular weight of 5000 to 1 million daltons), licochalcone A and mixtures thereof.
- flavone glycosides such as e.g. ⁇ -Glucosylrutin, carnitine, polydocanol
- Formulations according to the invention which contain one or more anti-wrinkle active ingredients such as flavone glycosides, in particular ⁇ -glycosyl rutin, coenzyme Q10, retinol and its esters, vitamin E and its derivatives, and other anti-wrinkle active ingredients known to the person skilled in the art, are particularly suitable for protecting against aesthetically unattractive skin changes such as, for example, those which are tired Skin or aging. These changes include e.g.
- the emulsions according to the invention are furthermore advantageously suitable against the appearance of dry or rough skin.
- antioxidants can be selected from the group comprising amino acids and their derivatives such as glycine, histidine, tyrosine and tryptophan, imidazoles and their derivatives such as urocanic acid, peptides and their derivatives such as D, L-carnosine, D- Carnosine, L-carnosine and anserine, carotenoids, carotenes and their derivatives such as ⁇ -carotene, ⁇ -carotene and lycopene, lipoic acid and their derivatives such as dihydroliponic acid, aurothioglucose, propylthiouracil and other thiols and their salts such as thioredoxin, glutathione, cysteine , Cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl, lauryl,
- ⁇ -hydroxy fatty acids palmitic acid, phytic acid and lactoferrin
- ⁇ -hydroxy acids such as citric acid, lactic acid and malic acid, Humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives such as ⁇ -linolenic acid, linoleic acid and oleic acid, folic acid and their derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and its derivatives such as eg ascorbyl palmitate, Mg-ascorbyl phosphate and ascorbyl acetate, tocopherols and their derivatives such as vitamin E acetate, vitamin A and its derivatives such as vitamin A palmitate, konyferyl benzoate of benzoin, rutinic acid and its derivatives,
- the amount of the antioxidants (one or more compounds) in the formulations according to the invention is preferably 0.001 to 30% by weight, particularly preferably 0.05 to 20% by weight, in particular 0.1 to 10% by weight, based on the Total weight of the preparation.
- vitamin E or its derivatives represent the antioxidant or antioxidants
- vitamin A, vitamin A derivatives, carotenes or their derivatives represent the antioxidant or antioxidants
- the cosmetic emulsions according to the present invention contain cosmetic active ingredients, preferred active ingredients being antioxidants which can protect the skin from oxidative stress.
- substances are used to improve the microbial stability, in particular substances with an antimicrobial effect, in particular against bacteria, yeasts and fungi.
- Benzoic acid, its esters and salts, propionic acid and its salts, salicylic acid and its salts, 2,4-hexadienoic acid (sorbic acid) and its salts, formaldehyde and paraformaldehyde, 2-hydroxydiphenyl, zinc pyrithione, inorganic sulfites and bisulfites are to be mentioned as preferred.
- Chlorobutanolum 4-hydroxybenzoic acid, its salts and esters, 3-acetyl-6-methyl-2,4 (3H) -pyranedione (dehydroacetic acid) and its salts, formic acid and its sodium salt, 1,6-bis (4-amidino-2 -bromphenoxy) -n-hexane (dibromohexamidine) and its salts, ethyl mercury (II) thiosalicylic acid, sodium salt (thiomersalum), phenyl mercury and its salts, 10-undecylenic acid and its salts, 5-amino-1,3-bis (2 -ethylhexyl) -5-methyl-hexahydropyrimidine (Hexetidinum), 5-bromo-5-nitro-1,3-dioxane, 2-bromo-2-nitro-1,3-propanediol (bronopol), 2,4-dichlorobenzyl alcohol, N- (4
- Methylisothiazolinones the combinations of ethyl lauryl arginate with phenoxyethanol, benzethonium chloride with phenoxyethanol or piroctone olamines with phenoxyethanol are particularly advantageous.
- the formulations according to the invention can contain further ingredients known in cosmetic formulations, such as, for example, acetyl trifluoromethylphenyl valylglycine, acrylamide / ammonium acrylate copolymer, acrylates / C12-22 alkyl methacrylate copolymer, aluminum / magnesium hydroxide stearates, ammonium lactates, ammonium polyacrylates, ammonium polyacryloyldimethyl taurates, Arginine PCA, Beerwax, Benzethonium chloride, Capryloyl Salicylic Acid, ⁇ -Carotin, Cinnamic Acid, Coco Glucoside, Copper Gluconate, Dehydroxanthan Gum, Diphenyl Dimethicone, Disodium Adenosine Triphosphate, Disodium Succinate, Disteardimoncata Hectorite, Citrated Efidate, False Diacidate, Citrate Hydrogenated Palm Kernel G
- substances to positively influence the odor of the formulation makes sense.
- these include e.g. Dipropylene glycol, methyl dihydrojasmonate, phenethyl alcohol, linalool, linalyl acetate, 2,6-dimethyl-7-octen-2-ol, alpha-hexylcinnamaldehyde, 2-acetonapthone-1,2,3,4,5,6,7, 8-octahydro-2,3,8,8-tetramethyl pt-butylalpha-methyldihydrocinnamic aldehyde, benzyl acetate, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta -gamma-2-benzopyran, methyl cedryl ketone, ethylene brassylate, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxyaldehyde,
- tapioca starch (Example 1) leads to a significant increase in the contact angle and thus indicates an increased water resistance.
- the formulation according to the invention feels just as light and fresh as a formulation without powder raw material (C2).
- the formulation according to the invention shows better masking of the oils than the other formulations (C1 and C2).
- the formulations with powder raw materials (Ex. 1 and C1) have a smoother skin feel than the formulation without powder raw material (C2).
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Description
- Die vorliegende Erfindung betrifft eine kosmetische Zubereitung mit UV-Filtern, Silikonelastomergelen und Tapiokastärke.
- Der Wunsch, schön und attraktiv auszusehen, ist von Natur aus im Menschen verwurzelt. Auch wenn das Schönheitsideal im Laufe der Zeit Wandlungen erfahren hat, so ist das Streben nach einem makellosen Äußeren immer das Ziel der Menschen gewesen. Einen wesentlichen Anteil an einem schönen und attraktiven Äußeren hat dabei der Zustand und das Aussehen der Haut. Um diese jung und makellos zu halten werden seit vielen Jahren Hautpflegeprodukte eingesetzt.
- Anwender stellen an moderne Hautpflegeprodukte, speziell in Form von Cremes für die Anwendung im Gesicht, eine Reihe von Anforderungen. Sie sollen die Haut pflegen, insbesondere die Haut über einen langen Zeitraum mit Feuchtigkeit versorgen. Dieses wird in der Regel über "Moisturizer" realisiert, die Wasser im Stratum Corneum binden (z.B. Glycerin), zudem werden mit zugesetzten Lipiden die oberen Hautschuppen geschmeidig gehalten und der transepidermale Wasserverlust reduziert. Desweiteren erwarten die Anwender häufig eine Wirkung gegen die Anzeichen von Hautalterung, wie z.B. die Ausbildung von Falten, das Nachlassen der Hautelastizität oder die Entstehung von Altersflecken. Hierzu werden zum einen Wirkstoffe verwendet, die beispielsweise die Aktivität der Hautzellen stimulieren, aber auch verstärkt UV-Filter eingesetzt, die besonders die für die Hautalterung verantwortlichen UVA-Strahlen blockieren. Alle diese Inhaltsstoffe stellen eine große Herausforderung für eine angenehme Sensorik dar, da sie nach dem Verdunsten der flüchtigen Bestandteile der Formulierung als Film auf der Haut zurückbleiben, und dort sensorisch vom Verbraucher wahrgenommen werden. Die fühlbaren Rückstände werden dabei oft negativ beschrieben und verhindern das Gefühl dass das Produkt komplett in die Haut "eingezogen" sei.
- Um die durch die Formulierung und die Marktanforderungen benötigten Rückstände sensorisch attraktiver zu machen, wird eine Reihe von Sensorik-Additiven eingesetzt. Insbesondere Silikonverbindungen und Puderrohstoffe sind hierbei zu nennen, da sie das klebrige Gefühl von z.B. Glycerin oder die ölig/fettige Anmutung vieler Lipide oder UV-Filter maskieren können. Man findet in Produkten verstärkt den Einsatz von Silikonelastomeren, welches verschieden vernetzte und/oder modifizierte Polydimethylsiloxane sind, die in der Regel in einem Medium als Gel gequollen vorliegen. Dieses Medium ist bevorzugt ein niedrigviskoses, bevorzugt auch flüchtiges Silikon. Diese Rohstoffklasse liefert ein pudrig/trockenes, samtig/seidiges Hautgefühl nach dem Verteilen und kann, je nach Formulierungstyp, ölig/fettig und/oder klebrige Rohstoffe maskieren.
- Generell ist die angenehme Sensorik der Silikonelastomere in W/O Emulsionen stärker ausgeprägt als in O/W Emulsionen, da sie sich in diesem Fall in der äußeren, hydrophoben Phase aufhalten und somit unmittelbar sensorisch wahrgenommen werden können. Diese Formulierungen sind besonders reichhaltig und daher nicht für alle Verbraucher-Gruppen geeignet. Verbraucher, die eher normale bis Mischhaut haben, legen in der Regel deutlich weniger Wert auf ein reichhaltiges Produkt als Menschen mit trockener Haut. Das liegt besonders daran, dass die Reichhaltigkeit mit der Pflege und dem Schutz der Haut verbunden wird.
- Für Verbraucher mit normaler bis Mischhaut werden fast ausschließlich die weniger reichhaltigen O/W Emulsionen eingesetzt. In diesen Formulierungen ist der Effekt der Silikonelastomere aber deutlich schwächer ausgeprägt, weswegen in der Regel eine recht hohe Einsatzkonzentration benötigt wird. Werden in einem Medium die Cyclopentasiloxan gequollene Elastomergele eingesetzt, bedeutet dies, dass ein hoher Anteil von eben Cyclopentasiloxan in der Formel vorhanden ist, was sensorisch für den Verbraucher merkbar ist. Die Formulierungen fühlen sich künstlich an, da das Silikon deutlich spürbar ist.
- Es besteht Bedarf an einem leichten Gesichtspflegeprodukt für normale bis Mischhaut, welches mindestens einen Lichtschutzfaktor von 15 mit entsprechendem UVA-Schutz aufweist und bevorzugt mindestens 10% Glycerin enthält um den Verbrauchererwartungen in Bezug auf Schutz vor Hautalterung durch UV Strahlung und auf Feuchtigkeitsversorgung zu erfüllen. Das Produkt soll dabei schnell vollständig in die Haut einziehen und sich zu jeder Zeit natürlich anfühlen. Gewünschte Zusatznutzen sind z.B. eine effizient einstellbare Konsistenz zur Darreichung im Tiegel oder auch eine hohe Wasserfestigkeit, um die Produkteigenschaften z.B. auch beim Schwitzen oder anderen mit Wasser verbundenen Tätigkeiten zu behalten.
- Nachteilig am Stande der Technik ist insbesondere der Umstand, dass die Wasserfestigkeit UV-Filter haltiger Zubereitungen meist nur durch den Einsatz von Filmbildnern (z.B. Polyvinylpyrrolidon) gewährleistet werden kann. Der Einsatz solcher Filmbildner führt jedoch zu einem klebrig unangenehmen Hautgefühl. Bei der Anwendung am Strand führen solche Zubereitungen darüber hinaus zu einer erhöhten Sandanhaftung. Silikonelastomergele, die das Hautgefühl positiv beeinflussen, können diesen Effekt allenfalls unzureichend kompensieren.
- Es war daher die Aufgabe der vorliegenden Erfindung, die Wasserfestigkeit UV-Filter haltiger kosmetischer Zubereitungen zu erhöhen ohne (oder mit verringerter Einsatzkonzentration) auf die herkömmlichen Filmbildner zurückgreifen zu müssen. Dies gilt insbesondere für Silikonelastomergel haltige Zubereitungen.
- Ein weiteres technisches Problem bei der Formulierung kosmetischer Zubereitungen stellt die Einstellung der für den Anwendungszweck geeigneten Viskosität der Zubereitung dar. Häufig müssen die Zubereitungen erst mit Hilfe polymerer Verdickungsmittel, beispielsweise mit Hilfe von Polyacrylaten, auf die gewünschte Viskosität gebracht werden. Derartige Verdickungsmittel sind jedoch häufig sensorisch unattraktiv und führen bei der Auftragung auf die Haut zur Röllchenbildung.
- Es war daher die Aufgabe der vorliegenden Erfindung, die Viskosität kosmetischer Zubereitungen mit alternativen kosmetischen Inhaltsstoffen zu regulieren. Dies gilt insbesondere für UV-Filter und Silikonelastomergel haltige Zubereitungen.
- Gelöst werden die Aufgaben durch eine kosmetische Zubereitung enthaltend gemäß Anspruch 1. Vorteilhafte Eigenschaften liegen auch in der Verwendung von Tapiokastärke in kosmetischen Zubereitungen, enthaltend UV-Filter und Silikonelastomere zur Erhöhung der Wasserfestigkeit, der Erhöhung der Viskosität.
- Zwar kennt der Stand der Technik die
EP 0893987 ,EP 1139997 ,EP 1551923 ,EP 1731136 ,EP 1784158 , ,FR 2780642 ,FR 2862534 EP 0827983 ,US 2004/228888 ,US 2010/322877 ,US 4894222 ,US 2005/277768 ,US 2006/034876 ,US 2004/044121 ,US 5654362 sowieEP 1493421 , doch konnten diese Schriften nicht den Weg zur vorliegenden Erfindung weisen. Außerdem kennt der Fachmann dieEP 2181698 ,WO 2008/085360 ,US 6024944 ,EP 2255849 ,US 5945090 ,EP 2181699 sowie die Mintel GNPD Datenbank Einträge Nr. 1036175 und Eintrag Nr. 1548109, die ebenfalls nicht den Weg zur vorliegenden Erfindung weisen konnten. - Unter "erfindungsgemäß", "erfindungsgemäß vorteilhaft" etc. werden im Rahmen der vorliegenden Beschreibung Zubereitungen entsprechend der Ansprüche verstanden. Es ist erfindungsgemäß, wenn die Zubereitung in Form einer O/W-Emulsion vorliegt.
- Vorteilhafte Ausführungsformen der vorliegenden Erfindung sind dadurch gekennzeichnet, dass die Zubereitung mindestens 5 Gew.-%, bezogen auf das Gesamtgewicht der Zubereitung, an UV-Filtern enthält.
- Bei den erfindungsgemäß vorteilhaften Silikonelastomergelen handelt es sich um vernetzte, ggf. substituierte Organopolysiloxane, die in einem geeigneten Trägermedium gequollen sind. Die Vernetzung kann mittels aller gängigen Verfahren und Vernetzern durchgeführt worden sein. Trägermedien können z.B. cyclische oder lineare Silikone sowie organische Lipide sein.
- Als erfindungsgemäße Siloxanelastomere kommen insbesondere die folgenden Elastomere als erfindungsgemäß vorteilhafte Ausführungsformen in Frage:
- A) Siloxanelastomer, welches hergestellt wird durch das Hydrosilylierungs-Produkt von
- (1) einem linearen Alkenyl-Endgruppen aufweisenden Polyorganosiloxan der Formel:
Mvi aDxD vi yM2-a
worin x eine Zahl von 450 bis 1250, y eine Zahl von 0 bis 200, a eine Zahl von 0 bis 2 ist, unter der Einschränkung dass a+y im Bereich von 1 bis 20 liegt, wobei Mvi definiert ist als
R1R2R3SiO1/2
worin R1 ein einwertiger ungesättigter Kohlenwasserstoffrest mit 2 Kohlenstoffatomen ist und R2 und R3 jeweils unabhängig einwertige C1bis C40-Kohlenwasserstoffreste sind, wobei D definiert ist als
R4R5SiO2/2
worin R4 und R5 jeweils unabhängig einwertige C1-40-Kohllenstoffreste sind, wobei Dvi definiert ist als
Dvi= R6R7SiO2/2
worin R6 ein einwertiger ungesättigter Kohlenwasserstoffrest mit 2 bis 10 Kohlenstoffatomen ist und R7 unabhängig ein einwertiger C1-40-Kohlenwasserstoffrest ist, wobei M definiert ist als
M = R8R9R10SiO1/2
worin R8, R9 und R10 jeweils unabhängig ein einwertiger C1-40-Kohlenwasserstoffrest ist und - (2) einem Harz der Formel:
(MH wQz)j
worin Q die Formel SiO4/2 hat und MH definiert ist als:
HbR11 3-bSiO1/2
worin R11 ein einwertiger C1-40-Kohlenwasserstoffrest ist, wobei b eine Zahl von 1 bis 3 ist und w und z ein Verhältnis von 0,5 bis 4,0 haben und j im Bereich von 2,0 bis 100 liegt, wobei die Hydrosilylierung in Gegenwart von - (3) Decamethylcyclopentasiloxan durchgeführt wird.
EP 0827983 , welche die erfindungsgemäßen Siloxanelastomere beschreibt, doch konnte diese Schrift nicht den Weg zur vorliegenden Erfindung weisen.
Erfindungsgemäß besonders bevorzugt ist dieses Siloxanelastomere sind dadurch gekennzeichnet, dass
R1 und R6 = (CH2=CH) sowie
R2, R3, R4, R5, R7, R8, R9 und R10 = CH3 darstellen.
Das erfindungsgemäße Siloxanelastomere kann beispielsweise bei der Firma Momentive Performance Materials unter der Handelsbezeichnung Silsoft Silicone Gel erworben werden.
Es ist erfindungsgemäß vorteilhaft, wenn dieses erfindungsgemäße Siloxanelastomere A) in einer Konzentration von 5 bis 25 Gew.-% und bevorzugt in einer Konzentration von 10 bis 15 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Zusammensetzung, eingesetzt wird. - (1) einem linearen Alkenyl-Endgruppen aufweisenden Polyorganosiloxan der Formel:
- B) Siloxanelastomers, welches hergestellt wird durch die Reaktion
- (A) eines ≡Si-H enthaltenden Polysiloxans der Formel R3SiO(R'2SiO)a(R"HSiO)bSiR3 und, optional eines ≡Si-H enthaltenden Polysiloxans der Formel HR2SiO(R'2SiO)cSiR2H oder der Formel HR2SiO(R'2SiO)a(R"HSiO)bSiR2H,
mit R, R' und R" = Alkylgruppen mit 1 bis 6 C-Atomen,
a=0-250 , b=1-250, und c=0-250, - (B) mit einem alpha, omega-Dien der Formel CH2=CH(CH2)xCH=CH2 mit x=1-20, wobei die Reaktion ausgeführt wird in Gegenwart eines Platin-Katalysators und (C) eines Lösungsmittels gewählt aus der Gruppe bestehend aus (i) organischen Komponenten, (ii) Komponenten enthaltend ein Silikonatom und deren beliebigen Mischungen,
wobei die Reaktion solange durchgeführt wird, bis ein Gel durch Quervernetzung entstanden ist durch die Addition von ≡Si-H an die Doppelbindungen des alpha,omega-Diens.
Zwar kennt der Stand der Technik dieUS 5654362 , welche die erfindungsgemäßen Siloxanelastomere beschreibt, doch konnte diese Schrift nicht den Weg zur vorliegenden Erfindung weisen.
Es ist erfindungsgemäß vorteilhaft, wenn dieses erfindungsgemäße Siloxanelastomere B) in einer Konzentration von 5 bis 25 Gew.-% und bevorzugt in einer Konzentration von 10 bis 15 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Zusammensetzung, eingesetzt wird. - C) Erfindungsgemäß am meisten bevorzugt ist das Siloxanelastomer mit der folgenden Struktur:
Mit
R1= C1 bis C30 Alkylrest, R2=Wasserstoff,
R3= eine Quervernetzung -E-Y-E-, bei dem das andere Ende der Quervernetzung mit einer zweiten Silikonelastomerkette verbunden ist, jedes E eine bivalente Gruppe darstellt gewählt aus den Gruppen -CH2-CH2- oder -CH=CH- und Y eine bivalente Kohlenwasserstoff-Gruppe, ein Siloxan oder eine Kombination aus beidem darstellt,
a = 265-2000, b= 0-249, C= 1-250, mit der Vorgabe, dass b+c ≤ 250,
das in einem Lösungsmittel gequollen ist.
Bei diesem Siloxanelastomer ist es erfindungsgemäß bevorzugt, wenn R3 gewählt wird aus Polyethern, Pentylen, Hexylen, Heptylen, Octylen, Nonylen, Decylen, Dodecylen, Tetradecylen und Mischungen davon.
Es ist bei diesem Siloxanelastomer erfindungsgemäß bevorzugt, wenn die Verbindung 0,01 bis 90 Mol-% Quervernetzer enthält.
Bei diesem Siloxanelastomer ist es erfindungsgemäß bevorzugt, wenn als Lösungsmittel Decamethylcyclopentasiloxan eingesetzt wird.
- (A) eines ≡Si-H enthaltenden Polysiloxans der Formel R3SiO(R'2SiO)a(R"HSiO)bSiR3 und, optional eines ≡Si-H enthaltenden Polysiloxans der Formel HR2SiO(R'2SiO)cSiR2H oder der Formel HR2SiO(R'2SiO)a(R"HSiO)bSiR2H,
- Das erfindungsgemäße Siloxanelastomer C) lässt sich erfindungsgemäß vorteilhaft nach dem folgenden Verfahren herstellen:
- 1) Umsetzen in Gegenwart eines Hydrosilylierungskatalysators von
- (a) einem ≡Si-H haltigen Polysiloxan mit der Formel
R1 3SiO(R1 2SiO)a(R1HSiO)dSiR1 3
worin jedes R1unabhängig voneinander eine monovalente Kohlenwasserstoffgruppe mit 1 bis 30 Kohlenstoffatomen ist, a gleich 265 bis 2000 ist und d gleich 1 bis 250 ist, mit - (b) Dien-, Diin- oder En-In-Verbindung,
wobei (a) und (b) in - (c) einem Verdünnungsmittel dispergiert sind, und
- (a) einem ≡Si-H haltigen Polysiloxan mit der Formel
- 2) Fortsetzen der Reaktion, bis ein Siliconelastomer durch Vernetzung und Addition von ≡Si-H an Doppelbindungen, in der Dien- Diin- oder En-In-Verbindung gebildet wird.
- Dabei ist es erfindungsgemäß bevorzugt, wenn ein zusätzliches zweites ≡Si-H-haltiges Polysiloxan vorhanden ist, das ausgewählt wird aus HR1 2SiO(R1 2SiO)eSiR1 2H, HR1 2SiO(R1 2SiO)a(R1HSiO)dSiR1 2H und Mischungen davon, worin jedes R1 unabhängig voneinander eine monovalente Kohlenwasserstoffgruppe mit 1 bis 30 Kohlenstoffatomen ist, a gleich 265 bis 2000 ist und d gleich 1 bis 250 ist und e gleich 0 bis 250 ist, wobei das zweite ≡Si-H haltige Polysiloxan in einem Molverhältnis von >0 bis 20 vorhanden sind.
- Erfindungsgemäß bevorzugt ist es ferner, wenn (b) ausgewählt wird aus 1,4-Pentadien, 1,5-Hexadien, 1,6-Heptadien, 1,7-Octadien, 1,8-Nonadien, 1,9-Decadien, 1,11-Dodecadien, 1,13-Tetradecadien und 1,19-Eicosadien, 1,3-Butadiin, 1,5-Hexadiin(Dipropargyl) und 1,Hexen-5-in.
- Erfindungsgemäß bevorzugt ist es nicht zuletzt, wenn das Molverhältnis von (a) zu (b) im Bereich von 0,7:1 bis 1,3:1 liegt.
- Diese erfindungsgemäßen Siloxanelastomere können beispielsweise bei der Firma Dow Corning unter der Handelsbezeichnung DC 9040, 9041 oder 9045 erworben werden.
- Es ist erfindungsgemäß vorteilhaft, wenn dieses erfindungsgemäße Siloxanelastomere C) in einer Konzentration von 5 bis 25 Gew.-% und bevorzugt in einer Konzentration von 10 bis 15 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Zusammensetzung, eingesetzt wird.
- Es ist erfindungsgemäß vorteilhaft, wenn die erfindungsgemäße Zubereitung einen oder mehrere weitere UV-Filter enthält, gewählt aus der Gruppe der Verbindungen 2-Phenylbenzimidazol-5-sulfonsäure und/oder deren Salze; Phenylen-1,4-bis-(2-benzimidazyl)-3,3'-5,5'-tetrasulfonsäuresalze; 1,4-di(2-oxo-10-Sulfo-3-bornylidenmethyl)-Benzol und dessen Salze; 4-(2-Oxo-3-bornylidenmethyl)benzolsulfonsäuresalze; 2-Methyl-5-(2-oxo-3-borny-lidenmethyl)sulfonsäuresalze; 2,2'-Methylen-bis-(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol); 2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]-phenol; 3-(4-Methylbenzyliden)campher; 3-Benzylidencampher; Ethylhexylsalicylat; Terephthalidendicamphersulfonsäure; 2-Ethylhexyl-2-cyano-3,3-diphenylacrylat; 4-(Dimethylamino)-benzoesäure(2-ethylhexyl)ester; 4-(Dimethylamino)benzoesäure-amylester; 4-Methoxybenzalmalon-säuredi(2-ethylhexyl)ester; 4-Methoxyzimtsäure(2-ethylhexyl)ester; 4-Methoxyzimtsäureisoamylester; 2-Hydroxy-4-methoxybenzophenon, 2-Hydroxy-4-methoxy-4'-methylbenzophenon; 2,2'-Dihydroxy-4-methoxybenzophenon; 2-(4'-Diethylamino-2'-hydoxybenzoyl)-benzoesäurehexylester; Homomenthylsalicylat; 2-Ethylhexyl-2-hydroxybenzoat; Dimethicodiethylbenzalmalonat; 3-(4-(2,2-bis Ethoxycarbonylvinyl)-phenoxy)propenyl)-methoxysiloxan / Dimethylsiloxan - Copolymer; Dioctylbutylamidotriazon (INCI: Diethylhexyl-Butamidotriazone); 2,4-bis-[5-1(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)-imino]-6-(2-ethylhexyl)-imino-1,3,5-triazin mit der (CAS Nr. 288254-16-0); 4,4',4"-(1,3,5-Triazin-2,4,6-triyltriimino)-tris-benzoësäure-tris(2-ethyl-hexylester) (auch: 2,4,6-Tris-[anilino-(p-carbo-2'-ethyl-1'-hexyloxy)]-1,3,5-triazin (INCI: Ethylhexyl Triazone); 2,4-Bis-{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazin; 2,4,6-Tribiphenyl-4-yl-1,3,5-triazin; Merocyanine; Titiandioxid; Zinkoxid.
- Es ist im Rahmen der Erfindung sinnvoll, Wirkstoffe zur positiven Beeinflussung der Altershaut, die die Entstehung von Falten oder auch bestehenden Falten vermindern, einzusetzen. Als besonders bevorzugte Wirkstoffe gelten daher Biochinone, insbesondere Ubichinon Q10, Isoflavon und Isoflavonoide, Genistein, Arctiin, Cardiolipin, Liponsäure, Anti Freezing Proteine, Hopfen- und Hopfen-Malz-Extrakte und/oder die Restrukturierung des Bindegewebes fördernde Stoffe, Isoflavonoide sowie Isoflavonoid-haltige Pflanzenextrakte wie z.B. Soja- und Klee-Extrakte, die auch in den erfindungsgemäßen Zubereitungen und Hautauflagenmatrices sehr gut verwendet werden können. Auch zeigte sich, dass sich das erfindungsgemäße Kombinationsprodukt in besonderer Weise eignet, Wirkstoffe zur Unterstützung der Hautfunktionen bei trockener Haut, wie beispielsweise Vitamin C, Biotin, Kreatin, Kreatinin, Propionsäure, Glycerin, Grüntee-Extrakte, white tea - Extrakte oder - Lösungen, zu verwenden. In ähnlicher Weise erwies sich die Einarbeitung von Wirkstoffen zur Linderung bzw. positiven Beeinflussung von irritativen Hautzuständen, sei es bei empfindlicher Haut im Allgemeinen oder bei durch Noxen gereizter Haut (UV-Licht, Chemikalien), als vorteilhaft. Hier sind Wirkstoffe zu nennen wie Sericoside, verschiedene Extrakte des Süssholzes, Licochalcone A, Silymarin bzw. Silyphos, Flavonoide, Dexpanthenol, Ethanol, Inhibitoren des Prostaglandinstoffwechsels, insbesondere der Cyclooxygenase, und des Leukotrienstoffwechsels, insbesondere der 5-Lipoxygenase, aber auch des 5-Lipoxygenase Inhibitor Proteins, FLAP. Auch erwies sich die Einarbeitung von Modulatoren der Pigmentierung als vorteilhaft. Hier sind Wirkstoffe zu nennen, die die Pigmentierung der Haut vermindern und so zu einer kosmetisch gewünschten Aufhellung der Haut führen und/oder das Auftreten von Altersflecken reduzieren und/oder bestehende Altersflecken aufhellen, wie Tyrosinsulfat, Vitamin C, Liponsäure und Liponamid, verschiedene Extrakte des Süssholzes, Kojisäure, Hydrochinon, Arbutin, Fruchtsäuren, insbesondere Alpha-Hydroxy-Säuren (AHAs), Bearberry (Uvae ursi), Ursolsäure, Ascorbinsäure, Grüntee-Extrakte, Aminoguanidin und/oder Pyridoxamin. In gleicher Weise erwiesen sich die erfindungsgemäßen Nahrungsergänzungsmittel, Zubereitungen oder Matrices als hervorragende Grundlage für Wirkstoffe, die eine verstärkte/schnellere Bräunung der Haut herbeiführen (Advanced Glycation Endproducts (AGE), Lipofuscine, Nukleinsäure-Oligonukleotide, Purine und Pyrimidine, NO-freisetzende Substanzen, sei es mit oder ohne Einfluss von UV-Licht.
- Für den Einsatz ebenfalls geeignete Wirkstoffe sind beispielsweise Folsäure, Phytoen, Harnstoff, D-Biotin, Coenzym Q10, Flavonglycoside wie z.B. α-Glucosylrutin, Carnitin, Polydocanol, natürliche und synthetische Isoflavonoide insbesondere Genistein, Flavonoide, Carotinoide, Kreatin, Kreatinin, Taurin, Ascorbinsäure sowie deren Derivate, Sauerstoff, Tocopherol sowie dessen Ester, Dihydroxyaceton, 8-Hexadecen-1,16-dicarbonsäure, langkettige Hyaluronsäuren (d.h. mit einem mittleren Molekulargewicht von 1 Million bis 3 Million Dalton) und kurzkettige Hyaluronsäuren (d.h. mit einem mittleren Molekulargewicht von 5000 bis 1 Million Dalton), Licochalcon A und deren Gemische. Derartige Inhaltsstoffe können jeweils in einer Einzelkonzentration von 0,01 bis 30 Gewichts-%, bezogen auf das Gesamtgewicht der Zubereitung, in dieser enthalten sein.
- Erfindungsgemäße Formulierungen, welche ein oder mehrere Antifaltenwirkstoffe wie Flavonglycoside insbesondere α-Glycosylrutin, Coenzym Q10, Retinol und dessen Ester, Vitamin E und dessen Derivate sowie andere dem Fachmann bekannte Antifaltenwirkstoffe enthalten, eignen sich insbesondere zum Schutz vor ästhetisch unattraktiven Hautveränderungen wie sie beispielsweise bei ermüdeter Haut oder der Hautalterung auftreten. Zu diesen Veränderungen gehören z.B. Trockenheit, Rauhigkeit und Ausbildung von Trockenheitsfältchen, Juckreiz, verminderte Rückfettung vor allem nach dem Waschen, sichtbare Gefäßerweiterungen wie Teleangiektasien oder Cuperosis, Schlaffheit und Ausbildung von Falten und Fältchen, lokale Hyper-, Hypo- und Fehlpigmentierungen wie Altersflecken, vergrößerte Anfälligkeit gegenüber mechanischem Stress wie Rissigkeit und andere dem Fachmann bekannte Veränderungen. Weiterhin vorteilhaft eignen sich die erfindungsgemäßen Emulsionen gegen das Erscheinungsbild der trockenen bzw. rauhen Haut.
- Weiterhin vorteilhaft ist der Einsatz von ein oder mehrere Antioxidantien in erfindungsgemäßen Rezepturen. Als geeignete Antioxidantien können ein oder mehrere Substanzen gewählt werden aus der Gruppe enthaltend Aminosäuren und deren Derivate wie z.B. Glycin, Histidin, Tyrosin und Tryptophan, Imidazole und deren Derivate wie z.B. Urocaninsäure, Peptide und deren Derivate wie z.B. D,L-Carnosin, D-Carnosin, L-Carnosin und Anserin, Carotinoide, Carotine und deren Derivate wie z.B. α-Carotin, β-Carotin und Lycopin, Liponsäure und deren Derivate wie z.B. Dihydroliponsäure, Aurothioglucose, Propylthiouracil und andere Thiole sowie deren Salze wie z.B. Thioredoxin, Glutathion, Cystein, Cystin, Cystamin sowie deren Glycosyl-, N-Acetyl-, Methyl-, Ethyl-, Propyl-, Amyl-, Butyl-, Lauryl-, Palmitoyl-, Oleyl-, γ-Linoleyl-, Cholesteryl - und Glycerylester, Dilaurylthiodipropionat, Distearylthiodipropionat, Thiodipropionsäure und deren Derivate wie Ester, Ether, Peptide, Lipide, Nukleotide, Nukleoside und Salze, Sulfoximinverbindungen wie z.B. Buthioninsulfoximine, Homocysteinsulfoximin, Buthioninsulfone, Penta-, Hexa- und Heptathioninsulfoximin in sehr geringen verträglichen Dosierungen (z.B. pmol bis µmol/kg), ferner (Metall)-Chelatoren wie z.B. α-Hydroxyfettsäuren, Palmitinsäure, Phytinsäure und Lactoferrin, α-Hydroxysäuren wie z.B. Zitronensäure, Milchsäure und Apfelsäure, Huminsäure, Gallensäure, Gallenextrakte, Bilirubin, Biliverdin, EDTA, EGTA und deren Derivate, ungesättigte Fettsäuren und deren Derivate wie z.B. γ-Linolensäure, Linolsäure und Ölsäure, Folsäure und deren Derivate, Ubichinon und Ubichinol und deren Derivate, Vitamin C und dessen Derivate wie z.B. Ascorbylpalmitat, Mg-Ascorbylphosphat und Ascorbylacetat, Tocopherole und deren Derivate wie z.B. Vitamin E-Acetat, Vitamin A und dessen Derivate wie z.B. Vitamin A-Palmitat, Konyferylbenzoat des Benzoeharzes, Rutinsäure und deren Derivate, Ferulasäure und deren Derivate, Butylhydroxytoluol, Butylhydroxyanisol, Nordihydroguajakharzsäure, Nordihydroguajaretsäure, Trihydroxybutyrophenon, Harnsäure und deren Derivate, Mannose und deren Derivate, Zink und dessen Derivate wie z.B. ZnO und ZnSO4, Selen und dessen Derivate wie z.B. Selenmethionin, Stilbene und deren Derivate wie z.B. Stilbenoxid und trans-Stilbenoxid, sowie die erfindungsgemäß geeigneten Derivate der genannten Wirkstoffe wie Salze, Ester, Ether, Zucker, Nukleotide, Nukleoside, Peptide oder Lipide.
- Die Menge der Antioxidantien (eine oder mehrere Verbindungen) in den erfindungsgemäßen Formulierunge beträgt vorzugsweise 0,001 bis 30 Gew.-%, besonders bevorzugt 0,05 bis 20 Gew.-%, insbesondere 0,1 bis 10 Gew.-%, bezogen auf das Gesamtgewicht der Zubereitung. Sofern Vitamin E oder dessen Derivate das oder die Antioxidantien darstellen, ist vorteilhaft, deren jeweilige Konzentrationen aus dem Bereich von 0,001 bis 10 Gew.-%, bezogen auf das Gesamtgewicht der Zubereitung, zu wählen. Sofern Vitamin A, Vitamin-A-Derivate, Carotine oder deren Derivate das oder die Antioxidantien darstellen, ist vorteilhaft, deren jeweilige Konzentrationen aus dem Bereich von 0,001 bis 10 Gew.-%, bezogen auf das Gesamtgewicht der Zubereitung, zu wählen. Es ist insbesondere vorteilhaft, wenn die kosmetischen Emulsionen gemäß der vorliegenden Erfindung kosmetische Wirkstoffe enthalten, wobei bevorzugte Wirkstoffe Antioxidantien sind, welche die Haut vor oxidativer Beanspruchung schützen können.
- Es ist weiterhin im Rahmen der Erfindung vorteilhaft, wenn Substanzen zur verbesserung der mikrobioligischen Stabilität, insbesondere Substanzen mit antimikrobieller Wirkung, insbesonderer gegen Bakterien, Hefen und Pilze, eingesetzt werden. Als bevorzugt zu nennen sind hierbei Benzoesäure, ihre Ester und Salze, Propionsäure und ihre Salze, Salicylsäure und ihre Salze, 2,4-Hexadiensäure (Sorbinsäure) und ihre Salze, Formaldehyd und Paraformaldehyd, 2-Hydroxydiphenyl, Zinkpyrithion, Anorganische Sulfite und Bisulfite, Chlorobutanolum, 4-Hydroxybenzoesäure, ihre Salze und Ester, 3-Acetyl-6-methyl-2,4(3H)-pyrandion (Dehydracetsäure) und seine Salze, Ameisensäure und ihr Natriumsalz, 1,6-Bis(4-amidino- 2-bromphenoxy)-n-hexan (Dibromhexamidin) und seine Salze, Ethylquecksilber-(II)-thiosalicylsäure, Natriumsalz (Thiomersalum), Phenylquecksilber und seine Salze, 10-Undecylensäure und ihre Salze, 5-Amino-1,3-bis(2-ethylhexyl)-5-methyl-hexahydropyrimidin (Hexetidinum), 5-Brom-5-nitro-1,3-dioxan, 2-Brom-2-nitro-1,3-propandiol (Bronopol), 2,4-Dichlorbenzylalkohol, N-(4-Chlorphenyl)-N'-(3,4-dichlorphenyl)-harnstoff (Triclocarban), 4-Chlorm-cresol, 2,4,4'-Trichlor-2'-hydroxydiphenylether (Triclosanum), 4-Chlor-3,5-dimethylphenol, 1,1'-Methylenbis(3-(1-hydroxymethyl-2,5-dioximidazolidin-4-yl)harnstoff) (Imidazolidinylharnstoff), Poly(hexamethyl-endiguanid)hydrochlorid, 2-Phenoxy-ethanol, Hexamethylentetramin, 1-(3-Chlorallyl)-3,5,7-triaza-1-azonia-adamantanchlorid, 1-(4-Chlorphenoxy)-1-(imidazol-1-yl)-3,3-dimethyl-2-butanon, 1,3-Bis-(hydroxymethyl)-5,5-dimethyl-2,4-imidazolidindion, Benzylalkohol, 1-Hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2-pyridon und sein Monoethanolaminsalz, 2,2'-Methylen-bis(6-brom-4-chlorphenol) (Bromchlorophen), 3-Methyl-4-(1-methylethyl)phenol, Mischung von 5-Chlor-2-methyl-3(2H)-isothiazolon und 2-methyl-3(2H)-isothiazolon mit Magnesiumchlorid und Magnesiumnitrat, 2-Benzyl-4-chlorphenol (Chlorophenum), 2-Chloracetamid, Chlorhexidin, sein Acetat, Gluconat und Hydrochlorid, 1-Phenoxy-propan-2-ol, N-Alkyl (C12-C22)trimethylammoniumbromid und -chlorid, 4,4-Dimethyl-1,3-oxazolidin, N-Hydroxymethyl-N-(1,3-di(hydroxymethyl)-2,5-dioxoimidazolidin-4-yl)-N'-hydroxymethyl-harnstoff, 1,6-Bis(4-amidinophenoxy)-n-hexan (Hexamidinum) und seine Salze, Glutaraldehyd (Pentan-1,5-dial), 5-Ethyl-1-aza-3,7-dioxabicyclo(3.3.0)octan, 3-(4-Chlorphenoxy)-1,2-propandiol (Chlorphenesin), Natriumhydroxymethylaminoacetat, Silberchlorid, Benzethoniumchlorid, Benzalkoniumchlorid, -bromid und -saccharinat, Benzylhemiformal, lodopropinylbutylcarbamat (IPBC), 3-lod-2-propinylbutylcarbamat, 2-Methyl-3-(2H)-isothiazolon (Methylisothiazolinone), Piroctone Olamine und Ethyl lauroyl arginate. Insbesondere vorteilhaft sind Methylisothiazolinone, die Kombinationen von Ethyl lauryl arginate mit Phenoxyethanol, Benzethoniumchlorid mit Phenoxyethanol oder Piroctone Olamine mit Phenoxyethanol.
- Zudem können die erfindungsgemäßen Formulierungen weitere, in kosmetischen Formulierungen bekannte Inhaltsstoffe enthalten, wie z.B. Acetyl Trifluoromethylphenyl Valylglycine, Acrylamide / Ammonium Acrylate Copolymer, Acrylates/C12-22 Alkylmethacrylate Copolymer, Aluminum / Magnesium Hydroxide Stearate, Ammonium Lactate, Ammonium Polyacrylate, Ammonium Polyacryloyldimethyl Taurate, Arginine PCA, Beerwax, Benzethoniumchlorid, Capryloyl Salicylic Acid, β-Carotin, Cinnamic Acid, Coco Glucoside, Copper Gluconate, Dehydroxanthan Gum, Diphenyl Dimethicone, Disodium Adenosine Triphosphate, Disodium Succinate, Disteardimonium Hectorite, Dodecene, Eperua Falcata, Hydrogenated Palm Glycerides Citrate, Hydrogenated Palm Kernel Glycerides, Hydrolyzed Wheat Protein, PG-Propyl Methylsilanediol, Kasei, Kinetin, Hydroxyethyl Acrylate / Sodium Acryloyldimethyltaurate Copolymer, Isodeceth-6, Linseed Acid, Lutein, Lyopene, Magnesium Aspartate, Melibiose, Oxothiazolidinecarboxylic Acid, Palmitoyl Pentapeptide 4, PEG-8 Laurate, PG-10 Stearat, Phenethyl Alcohol, Phenylpropanol, Polyacrylate-13, Polyacrylate-3, Quinic Acid, Sarcosine, Saxifraga Sarmentosa Extract, Scutellaria Baicalensis Extract, Shikimic Acid, Sodium Metabisulfite, Soy Isoflavone, Tocopheryl Glucoside, Trideceth-6, Zeaxanthin, Zinc Gluconate, Triacetin, 1,2 Hexandiol, Hydroxyethylpiperazine Ethane Sulfonic Acid, Nicotinamide, Penethyl Alcohol, Penthylene Glycol, Carnaubau Wax, Chlorhexidine Digluconate, Oleyl Erucate, Acetyltrifluoromethylphenylvalylglycin, Acrylamidammoniumacrylatcopolymer, Aluminummagnesiumhydroxidstearat, Ammoniumlactat, Ammoniumpolyacrylat, Ammoniumpolyacryloyldimethyltaurat, Arginin PCA, Capryloylsalicylsäureester, Zimtsäure, Cocoglucosid, Kupfergluconat, Diphenyldimethicon, Dinatriumadenosintriphosphat, Dnatriumsuccinat, Disteardimoniumhectorit, Dodecen, Eperua Falcata , hydriertes Palmenglycerid, hydriertes Palmenglyceridcitrat, Hydrierte Palmenkernglyceride, Hydrolisiertes Weizenprotein PG-Propylmethylsilandiol, Hydroxyethylacrylat / Natriumacryloyldimethyltauracopolymer, Isodeceth-6, Linseed Acid, Magnesiumaspartat, Melibiose, Oxothiazolidinecarboxylsäure, Palmitoylpentapeptide 4, PEG-8 Laurat, Phenethylalkohol, Phenylpropanol, Polyacrylate-13, Polyacrylate-3 , Sarcosin, Saxifraga Sarmentosa Extrakt, Scutellaria Baicalensis Extrakt, Natriummetabisulfit, Sojaisoflavon, Tocopherylglucosid, Trideceth-6, Zinkgluconat, Triacetin, 1,2 Hexandiol, Hydroxyethylpiperazine Ethane Sulfonic Acid, Nicotinamide, Penethyl Alcohol, Penthylene Glycol, Carnaubau Wax, Chlorhexidine Digluconate, Oleyl Erucate.
- Zudem ist die Verwendung von Stoffen zur positiven Beeinflussung des Geruchs der Formuliuerung sinnvoll. Hierzu zählen z.B. Dipropylene glycol, Methyl dihydrojasmonate, Phenethyl alcohol, Linalool, Linalyl acetate, 2,6-Dimethyl-7-octen-2-ol, alpha-Hexylcinnamaldehyde, 2-Acetonapthone-1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl p-t-Butylalpha-methyldihydrocinnamic aldehyde, Benzyl acetate, 1,3,4,6,7,8-Hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyran, Methyl cedryl ketone, Ethylene brassylate, 4-(4-Hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxyaldehyde, Benzyl salicylate, Hexyl salicylate Orange oil, alpha-Isomethylionone, Diethyl phthalate, 4-t-Butylcyclohexyl acetate, Patchouli oil 3,7-Dimethyl-2,6-octadien-1-ol, Tetrahydrolinalool, Hydroxycitronellal, Isopropyl myristate, 3,7-Dimethyl-6-octen-1-ol, Orange terpenes, Heliotropin, Terpinyl acetate, omega-Pentadecalactone, Methyl-alpha-ionone, Lavandin oil, Lemon oil, Bergamot oil, 7-Acetyl-1,1,3,4,4,6-hexamethyltetralin, Coumarin, Ethyllinalool, Amyl salicylate, 2-tert-Pentyl-cyclohexyl acetate, 3-Methyl-5-phenyl-1-pentanol, Cedrol, Benzyl benzoate, Vanillin, alpha-Amylcinnamaldehyde, Dimethyl phthalate, d-Limonene, 2-Isobutyl-4-hydroxy-4-methyltetrahydropyran, Triethyl citrate, Terpineol, Lavender oil, Diethylene glycol monoethyl ether, 2-Phenoxyethyl isobutyrate, Anisyl alcohol, 3-Pentyltetrahydro(2H)pyranyl acetate, Methyl ester of rosin, partially hydrogenated, Isobornyl acetate, Rosemary oil, Petitgrain oil, 1,4-Dioxacyclohexadecane-5,16-dione, Isoamyl salicylate, gamma-Undecalactone, alpha-Ionone, Oxacyclohexadecen-2-one, 7-Octen-2-ol, 2-methyl-6-methylene, dihydro derive. 1,2-Propylene glycol, 3-(5,5,6-Trimethylbicyclo(2.2.1)hept-2-yl)cyclohexan-1-ol, Geranium oil, Musk ketone, Cedrenyl acetate, Isobornylcyclohexanol, lonone, Benzyl alcohol, gamma-Nonalactone, I-Menthol, Cyclohexyl salicylate, Dihydromyrcenyl acetate, Citral, Orange terpenes (natural), Cedarwood oil, alpha-Pinene, Majantol, Phenoxyethanol, Ethyl acetate, Cedrol methyl ether, 1,5,9-Trimethyl-13-oxabicyclo(10.1.0) trideca-4,8-diene, Peppermint oil, Eugenol, Ethyl maltol, Benzaldehyde, Cinnamic alcohol, 3,7-Dimethyl-1-octanol, alpha-Methyl-3,4-methylene dioxyhydrocinnamic aldehyde, beta-Pinene, d-Camphor, Methyl abietate, Cedryl acetate, Ylang ylang oil, Sandalwood oil, Mineral oil, Dimethyl benzyl carbinyl butyrate, Ethyl butyrate, Geranyl acetate, Hexylene glycol, Myrcene, alpha-Methyionantheme, beta-Ionone, 3-(4-t-Butylphenyl)propanal, 3,7-Dimethyloctan-3-yl acetate, Acetic acid, (1-oxopropoxy)-,1-(3,3-dimethylcyclohexyl), Eucalyptol, 4-Carvomenthenol, Stearic acid, Menthanyl acetate, Eucalyptus oil, Dihydroterpinyl acetate, o-t-Butylcyclohexyl acetate, Isoeugenol, alpha-Terpineol, Cyclamen aldehyde, Hydroxycitronellol, Myrcenyl acetate, Nopyl acetate, 3,7-Dimethyl-1,3,6-octatriene, Rhodinol, Dimethyl benzyl carbinyl acetate, Tricyclodecenyl propionate, 2-Methyl-5-phenylpentan-1-ol, Sclareoate, 3-Isocamphyl cyclohexanol, trans-Anethole, Hexahydro-4,7-methanoinden-5(6)-yl acetate, 4-(p-Hydroxyphenyl)-2-butanone, Nerolidol, alpha-Butylcinnamaldehyde, Bornyl acetate, Etyhl methylphenylglycidate, trans-betalonone, Camphene, Juniper berry oil, Mandarin oil, Nutmeg oil, Spearmint oil, Grapefruit oil, Labdanum oil, Galbanum oil, Menthone, Trichloromethyl phenyl carbinyl acetate, alpha-Methylbenzyl acetate, Ethyl-2methyl-1,3-dioxolane-2-acetate, 2,6-Nonadienal, Abietyl acetate, Anisic acid, Diphenyl ether, Triacetin, 2-Methyl-4-phenyl-2-butanol Phenylethyl acetate, 1-Phenyl-3-methyl-3-pentanol, Anisyl acetate, Cinnamic aldehyde, p-Methylanisole, 5-Phenylpentanol, Diethyl malonate, Citronellal, Nerol, Undecanal, 2-methyl-, Hexyl alcohol, Glyceryl caprylate, Methyl 2-nonenoate, Octyl acetate, Decanal, Lauryl alcohol, Lauric aldehyde, Ethyl vanillin, 3-Phenyl-1-propanol, Octanal, Butylated hydroxytoluene, 4-Acetyl-6-t-butyl-1,1-dimetylindane, delta-3-Caren, Benzyl laurate, Neryl acetate, Ethyl acetoacetate, Hexyl acetate, Menthol liquid, Citronellyl acetate, Tetrahydromyrcenol, Diacetin, Menthyl acetate, 3(4),8(9)-Dihydroxymethyl tricyclo(5.2.1.0(2,6)decane, 2,4-Dimethyl-3-cyclohexen-1-carboxaaldehyde, Cedrenol, Phenylacetaldehyde glyceryl acetal, Sabinene, 3,7,11-Trimethyl-1,2,10,-dodecatrien-3-ol (cis & trans), Octyldodecanol, Formaldehyde cyclododecyl ethyl acetal Myristicin, 3,7-Dimethyl-2(3),6-nonadienenitrile, Ethyllinylyl acetate, 2-Methylbutyl acetate, cis-3-Hexenyl salicylate, 2-Methyl-4-(2,6,6-trimethyl-2(1)-cyclohexen-1-yl) butanal, Maltol isobutyrate, 2-Methyl-3(4-(2-methylpropyl)phenyl)propanal, 12-Oxahexadecanolide, 1,1-Dimethoxy-2,25-trimethyl-4-hexene, 1,6,7,8-Tetrahydro-1,4,6,6,8,8-hexamthyl-as-indacen-3<2H>-one, Bergamot oil, bergaptene free, Treemoss abs., Citrus oil distilled, Lemon terpenes, gamma-Decalactone, 2-Methyl-4-phenyl-2-pentanone, Allyl phenoxyacetate, Methyl-delta-ionone, Citronella oil, Clove bud oil, Thyme oil, Lime oil, Bois de rose oil, Cognac oil, Neroli bigarade oil, Spike lavender oil, Vetiver oil, Fir needle oil, Methylpentenolone, Lemon oil terpenes, Isobutyl salicylate, beta-Caryophyllene, Pulegone, Thymol, gamma-Terpinene.
- Es wurden die in Tabelle 1 beschriebenen O/W Emulsionen zur Hautpflegehergestellt. Die Rezeptur #1 ist eine erfindungsgemäße Ausführungsform; die Beispiele C1 und C2 sind nicht erfindungsgemäße Vergleichsrezepturen. Alle Mengenangaben beziehen sich auf Gewichts-%.
Inhaltsstoff Bsp. #1 Bsp. C1 Bsp. C2 Glyceryl Stearate Citrate 2,5 2,5 2,5 Octocrylene 2 2 2 Ethylhexyl Salicylate 4 4 4 Butyl Methoxydibenzoylmethane 4 4 4 Butylene Glycol Dicaprylate/Dicaprate 2 2 2 Cyclomethicone + Cetearyl Dimethicone/Vinyl Dimethicone Crosspolymer1) 15 15 15 Tapioca Starch + Aqua 2 Dimethicone/Vinyl Dimethicone Crosspolymer + Silica 2) 2 Glycerin 10 10 10 Sodium Carbomer 0,6 0,6 0,6 Alcohol Denat. 5 5 5 Aqua ad 100 ad 100 ad 100 Actives eq. eq. eq. Preservative eq. eq. eq. Parfum eq. eq. eq. 1) Silsoft Silicone Gel (Momentive) - erfindungsgemäßes Silikonelastomergel 2) 9701 Cosmetic Powder (Dow Corninig) - nicht erfindungsgemäße Silikonelastomerpartikel - Bei 8 Probanden werden auf der gereinigten Unterarminnenseite pro Testprodukt 1,5 mg/cm2 Formulierung auf einer 4x6 cm großen Fläche appliziert. Nach 20 Minuten wird ein Wassertropfen von 8 µl aufgetropft. Dieser Tropfen wird nun betrachtet und mit einer CCD-Kamera aufgenommen. An dem in den Computer eingelesenen Bild wird eine Konturanalyse vorgenommen und durch Anlegen einer Tangente der Kontaktwinkel bestimmt. Ein hoher Kontaktwinkel steht dabei für eine hohe Wasserfestigkeit.
- Bsp.1: 62°
- Bsp. C1: 57°
- Bsp. C2: 53°
- Die Verwendung von Tapioca Stärke (Bsp. 1) führt zu einem signifikanten Anstieg des Kontaktwinkels und deutet so auf eine gesteigerte Wasserfestigkeit hin.
- Von allen drei Rezepturen wurde mit Hilfe eines Rotationsrheometers mit der Bezeichnung Rheomat R 123 der Firma proRheo GmbH mit dem Messkörper 1 bei einer Temperatur von 25°C bestimmt.
- Bsp. 1: >10000 mPas
- Bsp. C1: 8500 mPas
- Bsp. C2: 2800 mPas
- Beide Puderrohstoffe führen zu einer Erhöhung der Viskosität, wobei die erfindungsgemäße Formulierung hier noch deutlich effektiver ist.
- 10 geschulte Panelisten bewerten nach festgelegten sensorischen Attributen die Formulierungen. Dazu werden auf kreisrunden Arealen auf den Unterarminnenseiten 50 µl Produkt aufgetragen und in kreisenden Bewegungen (Takt von 1 Umdrehung pro Sekunde) verteilt. Es folgt eine Bewertung der sensorischen Attribute nach 20 Kreisen, nach vollständigem Einziehen sowie 5 Minunten nach dem Verteilen. Die Bewertung erfolgt auf einer Skala von 1 bis 10. Ein Unterschied von etwa 1 Punkt bedeutet nach den Erfahrungen ein vom ungeschulten Verbraucher merkbarer Unterschied.
- Parameter "Frisch/wässrig beim Verteilen"
- Bsp.1: 6,5
- Bsp. C1: 5,0
- Bsp. C2: 6,6
- Die erfindungsgemäße Formulierung fühlt sich beim Verteilen genau so leicht und frisch an wie eine Formulierung ohne Puderrohstoff (C2).
- Parameter "öliger Rückstand nach dem Verteilen"
- Bsp. 1: 2,2
- Bsp. C1: 2,5
- Bsp. C2: 3,2
- Die erfindungsgemäße Formulierung zeigt eine bessere Maskierung der Öle als die anderen Formulierungen (C1 und C2).
- Parameter "wachsig / stumpfes Hautgefühl 5 Minuten nach Verteilen"
- Bsp. 1: 1,6
- Bsp. C1: 1,7
- Bsp. C2: 2,5
- Die Formulierungen mit Puderrohstoffen (Bsp. 1 und C1) haben ein glatteres Hautgefühl als die Formulierung ohne Puderrohstoff (C2).
- Lediglich die erfindungsgemäße Formulierung zeigt eine leichte, frische Sensorik beim Verteilen, geringe ölige Rückstände auf der Haut und ein glattes Hautgefühl.
- Weitere erfindungsgemäße Formulierungen sind z.B.
Inhaltsstoff Bsp. #2 Bsp. #3 Bsp. #4 Bsp. #5 Bsp. #6 Glyceryl Stearate Citrate 2 2 Potassium Cetyl Phosphate 0,4 Polyglyceryl-3 Stearate 2 Sodium Stearoyl Glutamate 0,2 Cetearyl Alcohol 1 1 1 1 1 Octocrylene 2 2 2 2 2 Ethylhexyl Salicylate 4 4 4 4 4 Butyl Methoxydibenzoylmethane 4 2 2 4 4 Phenylbenzimidazole Sulfonic Acid 1 1 1 Butylene Glycol Dicaprylate/Dicaprate 2 2 2 2 2 Cyclomethicone + Cetearyl Dimethicone/Vinyl Dimethicone Crosspolymer 1) 15 15 15 Cyclomethicone + Dimethicone Crosspolymer 2) 15 15 Tapioca Starch + Aqua 2 2 2 2 2 Dimethicone/Vinyl Dimethicone Crosspolymer + Silica 3) Glycerin 10 10 10 10 10 Sodium Carbomer Carbomer 0,5 0,5 0,5 0,5 0,5 Sodium Hydroxide eq. eq. eq. eq. eq. Alcohol Denat. 5 5 5 Aqua ad 100 ad 100 ad 100 ad 100 ad 100 Actives eq. eq. eq. eq. eq. Preservative eq. eq. eq. eq. eq. Parfum eq. eq. eq. eq. eq. 1) Silsoft Silicone Gel (Momentive) - erfindungsgemäßes Silikonelastomergel 2) 9040 Silicone Elastomer Blend (Dow Corning) - erfindungsgemäßes Silikonelastomergel 3) 9701 Cosmetic Powder (Dow Corninig) - nicht erfindungsgemäße Silikonelastomerpartikel
Claims (7)
- Kosmetische Zubereitung in Form einer O/W-Emulsion enthaltenda) ein oder mehrere UV-Filterb) ein oder mehrere Silikoneiastomergele,
die Zubereitung mindestens 10 Gew.-%. bezogen auf das Gesamtgewicht der Zubereitung, an Silikonelastomergel enthält,c) mindestens 1,5 Gew.-%, bezogen auf das Gesamtgewicht der Zubereitung, an Tapiokastärke,dadurch gekennzeichnet, dass die Zubereitung 4-(tert,-Butyl)-4'-methCxydibenzoylmethan enthält. - Kosmetische Zubereitung nach Anspruch 1, dadurch gekennzeichnet, dass die Zubereitung mindestens 5 Gew.-%, bezogen auf das Gesamtgewicht der Zubereitung, an UV-Filtern enthält.
- Kosmetische Zubereitung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Zubereitung einen oder mehrere weitere UV-Filter enthält, gewählt aus der Gruppe der Verbindungen 2-Phenylbenzimidazol-5-sulfonsäure und/oder deren Salze; Phenylen-1,4-bis-(2-banzimidazyl)-3,3'-5,5'-tetrasuifonsäuresaize; 1,4-di(2-oxo-10-Sulfo-3-bornylidenmethyl)-Benzol und dessen Salze; 4-(2-Oxo-3-bornylidenmethyl)benzolsulfonsäuresafze; 2-Methyl-5-(2-oxo-3-bornylidenmethyl)sulfonsäuresalze; 2,2'-Methylen-bis-(6-(2H-benzotriazol-2-y))-4-(1,1,3,3-tetramethylbutyl)-phenol); 2-(2H-benzotriazol-2-yl)-4-methyl-6-[2-methyl-3-[1,3,3,3-tetramethyl-1-[(trimethylsily)oxy]disiloxanyl]propyl]-phenol; 3-(4-Methytbenzyliden)campher; 3-Benzylidencampher; Ethylhexylsalicylat; Terephthalidendicamphersulfonsäure; 2-Ethylhexyl-2-cyano-3,3-diphenylacrylat; 4-(Dimethylamino)-benzoesäure(2-ethythexyl)ester; 4-(Dimethylamino)benzoesäureamylester; 4-Methoxybenzalmalon-säuredi(2-ethylhexyl)ester; 4-Meihoxyzimtsäure(2-ethylhexyl)ester; 4-Methoxyzimtsäureisoemylester; 2-Hydroxy-4-methoxybenzophenon, 2-Hydroxy-4-methoxy-4'-methylbenzophetion; 2,2'-Dihydroxy-4-methoxybenzophenon; 2-(4'-Diethylamino-2'-hydoxybenzoyl)-benzoesäurehexylester; Homomenthylsalicylat; 2-Ethylhexyl-2-hydroxybenzoat; Dimethicodiethylbenzalmatonat; 3-(4-(2,2-bis Ethoxycarbonylvinyl)-phenoxy)propenyl)-methoxysiloxan / Dimethylsiloxan-Copolymer; Dioctylbutylamidotriazon (INCI: Diethylhexyl-Butamidotriazone); 2,4-bis-[5-1(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)-imino]-6-(2-ethylhexyl)-imino-1,3,5-triazin mit der (CAS Nr. 288254-16-0); 4.4'.4"-(1,3,5-Triazin-2.4,6.triyltrimino)-tris-benzoësäure-tris-(2-ethylhexylester) (auch: 2,4,6-Tris-[anilino-(p-carbo-2'-ethyl-1'-hexyloxy)]-1,3,5-triazin (INCI: Ethylhexyl Triazone); 2.4-Bis-[4-(2-ethyl-hexyloxy)2-hydroxy]-phenyl)-6-(4-methoxyphenyl)-1.3,5-triazin; 2,4,6-Tribiphenyl-4-yl-1,3,5-triaziri; Merocyanine; Titiandioxid; Zinkoxid.
- Kosmetische Zubereitung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Siloxanelastomer hergestellt wird durch das Hydrosilylierungs-Produkt von(1) einem linearen Alkenyl-Endgruppen aufweisenden Polyorganosiloxan der Formel:
Mvi sDxDvi yM2-a
worin x eine Zahl von 450 bis 1250, y eine Zahl von 0 bis 200, a eine Zahl von 0 bis 2 ist, unter der Einschränkung dass a+y im Bereich von 1 bis 20 liegt, wobei Mvi definiert ist als
R1R2R3SiO1/2
worin R1 ein einwertiger ungesättigter Kohlenwasserstoffrest mit 2 Kohlenstoffatomen ist und R2 und R3 jeweils unabhängig einwertige C1 bis C40-Kohlenwasserstoffreste sind, wobei D definiert ist als
R4R5SiO2/2
worin R4 und R3 jeweils unabhängig einwertige C1-40-Kohllenstoffreste sind, wobei Dvi definiert ist als
Dvi=R6R7SiO2/2
worin R6 ein einwertiger ungesättigter Kohlenwasserstoffrest mit 2 bis 10 Kohlenstoffatomen ist und R7 unabhängig ein einwertiger C1-40-Kohlenwasserstoffrest ist, wobei M definiert ist als
M = R8R9R10SiO1/2
worin R8, R9 und R10 jeweils unabhängig ein einwertiger C1-40-Kohlenwasserstofirest ist
und(2) einem Harz der Formel:
(MH wOz)j
worin Q die Formel SiO4/2 hat und MH definiert ist als:
HbR11 3-bSiO1/2
worin R11 ein einwertiger C1-40-Kohlenwasserstoffrest ist, wobel b eine Zahl von 1 bis 3 ist und w und z ein Verhältnis von 0,5 bis 4,0 haben und j im Bereich von 2,0 bis 100 liegt,
wobei die Hydrosilylierung in Gegenwart von(3) Decamethylcyclopentasiloxan durchgeführt wird. - Kosmetische Zubereitung nach Anspruch 6 dadurch gekennzeichnet, dass
R1 und R6 = (CH2=CH) sowie
R2, R3, R4, R5, R7, R8, R9 und R10 = CH3 darstellen. - Kosmetische Zubereitung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das Siloxanelastomer die folgende Struktur aufweist:
mitR1= C1 bis C30 Alkylrest, R2=Wasserstoff,R3= eine Quervernetzung -E-Y-E-, bei dem das andere Ende der Quervernetzung mit einer zweiten Silikonelastomerkette verbunden ist, jedes E eine bivalente Gruppe darstellt gewählt aus den Gruppen -CH2-CH2- oder -CH=CH- und Y eine bivalente Kohlenwasserstoff-Gruppe, ein Siloxan oder eine Kombination aus beidem darstellt, a = 265-2000, b= 0-249, C= 1-2-50, mit der Vorgabe, dass b+c ≤250,das in einem Lösungsmittel gequollen ist. - Kosmetische Zubereitung nach Anspruch 8, dadurch gekennzeichnet, dass bei dem Siloxanelastomer R3 gewählt wird aus Polyethern, Pentylen, Mexylen, Heptylen, Octylen, Nonylen, Decylen, Dodecylen, Tetradecylen und Mischungen davon.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102011078100A DE102011078100A1 (de) | 2011-06-27 | 2011-06-27 | Taptiokastärke in Silikonelastomer-haltigen kosmetischen Zubereitungen |
| PCT/EP2012/061474 WO2013000738A2 (de) | 2011-06-27 | 2012-06-15 | Taptiokastärke in silikonelastomer-haltigen kosmetischen zubereitungen |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP2723312A2 EP2723312A2 (de) | 2014-04-30 |
| EP2723312B1 EP2723312B1 (de) | 2017-10-04 |
| EP2723312B2 true EP2723312B2 (de) | 2020-03-18 |
Family
ID=46298422
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP12727667.3A Not-in-force EP2723312B2 (de) | 2011-06-27 | 2012-06-15 | Tapiokastärke in silikonelastomer-haltigen kosmetischen zubereitungen |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP2723312B2 (de) |
| DE (1) | DE102011078100A1 (de) |
| ES (1) | ES2654952T3 (de) |
| WO (1) | WO2013000738A2 (de) |
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| US11390821B2 (en) | 2019-01-31 | 2022-07-19 | Afton Chemical Corporation | Fuel additive mixture providing rapid injector clean-up in high pressure gasoline engines |
| US12024686B2 (en) | 2022-09-30 | 2024-07-02 | Afton Chemical Corporation | Gasoline additive composition for improved engine performance |
| US12043808B2 (en) | 2021-12-28 | 2024-07-23 | Afton Chemical Corporation | Quaternary ammonium salt combinations for injector cleanliness |
| US11873461B1 (en) | 2022-09-22 | 2024-01-16 | Afton Chemical Corporation | Extreme pressure additives with improved copper corrosion |
| US12134742B2 (en) | 2022-09-30 | 2024-11-05 | Afton Chemical Corporation | Fuel composition |
| US11795412B1 (en) | 2023-03-03 | 2023-10-24 | Afton Chemical Corporation | Lubricating composition for industrial gear fluids |
| US12454653B2 (en) | 2023-12-11 | 2025-10-28 | Afton Chemical Corporation | Gasoline additive composition for improved engine performance |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP2723312A2 (de) | 2014-04-30 |
| ES2654952T3 (es) | 2018-02-15 |
| WO2013000738A2 (de) | 2013-01-03 |
| EP2723312B1 (de) | 2017-10-04 |
| WO2013000738A3 (de) | 2013-12-05 |
| DE102011078100A1 (de) | 2012-12-27 |
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